Process for manufacturing paper using a base copolymer that has reacted with an aldehyde as a dry strength, retention, drainage and runnability aid

ABSTRACT

Process for manufacturing a sheet of paper and/or of paperboard and the like, according to which, the cellulosic material is brought into contact with at least one dry strength aid, characterized in that said dry strength aid is a cationic or amphoteric (co)polymer derived from the reaction between at least one aldehyde and at least one base (co)polymer comprising at least one nonionic monomer, said base copolymer being modified with at least one polyfunctional compound comprising at least three heteroatoms chosen from N, S, O and P, in which at least three of these heteroatoms each have at least one mobile hydrogen.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/373,069, filed on Jul. 18, 2014, which is a national stage filingunder section 371 of International Application No. PCT/FR2013/050390,filed on Feb. 26, 2013, and published on Sep. 6, 2013 as WO 2013/128109A1, and claims priority to French Application No. 1251740 filed on Feb.27, 2012. The entire disclosures of each of the prior applications arehereby incorporated herein by reference.

The invention relates to a novel process for manufacturing paper using,as dry strength, retention, drainage and runnability aid, a productderived from the reaction between at least one aldehyde and at least onecationic or amphoteric base (co)polymer, said copolymer comprisingacrylamide or derivative and incorporating, at its very heart, at leastone polyfunctional compound comprising at least three heteroatoms, inwhich at least three of these heteroatoms each have at least one mobilehydrogen.

Document WO 2011/15783 by the applicant describes polymers obtained byHofmann degradation reaction on a base (co)polymer. The base copolymercontains a polyfunctional compound incorporated during thepolymerization of the base (co)polymer. These compounds are used in themanufacture of paper as a flocculation, retention and/or drainage aid.

Document US 2011/0056640 describes a process for manufacturing paperusing a compound derived from the reaction between an aldehyde and anacrylamide/diallyldimethylammonium chloride copolymer. This process onlyimproves the drainage.

The document WO2010/059946 and US2006/0270801 describe a mixture ofcompounds to improve resistance of paper. Such mixtures include aglyoxalated polymer, and optionally a polyfunctional compound.

Document WO2005/072185 describes a method of paper making using polymerwhich have reacted with an aldehyde.

Document WO2007/041380 describes a wet strength agent consisting of amixture of glyoxalated polymers.

The problem addressed by the invention is to develop a novel process formanufacturing paper in which both the drainage properties and thephysical properties of the paper are improved.

DESCRIPTION OF THE INVENTION

The applicant has found and developed a novel process for manufacturinga sheet of paper and/or card and the like, according to which, before orafter formation of said sheet, the cellulosic material is brought intocontact with at least one additive.

The process is characterized in that said additive is a cationic oramphoteric (co)polymer derived from the reaction between at least onealdehyde and at least one base (co)polymer comprising at least onenonionic monomer selected from the group consisting of acrylamide(and/or methacryl amide), N,N-dimethylacrylamide, and/or acrylonitrile,said base copolymer being modified beforehand with at least onepolyfunctional compound comprising at least three heteroatoms chosenfrom N, S, O and P, in which at least three of these heteroatoms eachhave at least one mobile hydrogen.

In the remainder of the description and in the claims, the followingdefinitions apply:

-   -   additive denotes an aid that is simultaneously a dry strength        aid, a retention aid, a drainage aid and a runnability aid,    -   base (co)polymer denotes the (co)polymer before the reaction        with the aldehyde compound,    -   final (co)polymer denotes the product derived from the reaction        between the aldehyde compound and the base (co)polymer.

According to the invention, the modification of the base (co)polymerwith at least one additional polyfunctional compound consists either inincorporating the additional polyfunctional compound(s) before or duringthe polymerization of the constituent comonomers of the base(co)polymer, or in grafting the additional polyfunctional compound(s) tothe base (co)polymer.

Advantageously, when the polyfunctional compound is incorporated priorto or during the polymerization process, it does not react with thenon-ionic monomer selected from the group comprising acrylamide (and/ormethacrylamide), N, N dimethylacrylamide, and/or acrylonitrile. Indeed,the nonionic monomer is added into the reaction medium under thepolymerization conditions.

The polyfunctional compounds may be: oligomers, polymers, orcarbon-based chains comprising at least three carbon atoms.

The polyfunctional compound may be a polymer derived from “template”polymerization. These are polymers into which, during their synthesis, alow molecular weight polymer that will absorb one of the monomers takingpart in the polymerization is introduced.

In particular, the polyfunctional compounds referred to as additionalpolyfunctional compounds are selected from the group consisting ofpolyethyleneimines (PEI), polyamines (primary and secondary),polyallylamines, polythiols, polyalcohols, polyamide-epichlorohydrin(PAE) resins and polyamine amides (PAA).

The final cationic or amphoteric (co)polymer therefore comprises atleast one nonionic monomer selected from the group consisting ofacrylamide (and/or methacrylamide), N,N-dimethylacrylamide, and/oracrylonitrile, and is modified, prior to the reaction with an aldehydecompound, by at least one additional polymer selected from the groupconsisting of polyethyleneimine, polyamine (primary or secondary),polyallylamine, polythiols, polyalcohols, polyamide-epichlorohydrin(PAE) resins and polyamine amides (PAA).

In one preferred embodiment, the polyfunctional compound incorporated isselected from the group consisting of polyethyleneimine (PEI) andpolyamine amide (PAA).

In practice, the base (co)polymer contains at least 100 ppm ofpolyfunctional polymer, preferably at least 500 ppm, more advantageouslyat least 1000 ppm.

Advantageously, the aldehyde could be selected from the group consistingof glyoxal, glutaraldehyde, furandialdehyde, 2-hydroxyadipaldehyde,succinaldehyde, dialdehyde starch, 2,2-dimethoxyethanal, diepoxycompounds, and combinations thereof. Preferably the aldehyde compoundwill be glyoxal.

According to one preferred feature of the invention, the base(co)polymer is branched by means of a radical branching agent. In thiscase, the copolymer obtained is reacted with glyoxal.

The branching will preferably be carried out during the polymerizationof the base copolymer, in the presence of a polyfunctional radicalbranching agent and optionally a transfer agent. Below is a nonlimitinglist of branching agents: methylenebisacrylamide (MBA), ethylene glycoldiacrylate, polyethylene glycol dimethacrylate, diacrylamide,cyanomethyl acrylate, vinyloxyethyl acrylate or methacrylate andtriallylamine.

In practice, the branching agent is advantageously introduced in aproportion of five to fifty thousand (5 to 50 000) parts per million byweight relative to the active material, preferably 5 to 10 000,advantageously 5 to 5000 parts per million by weight. Advantageously,the branching agent is methylenebisacrylamide (MBA).

Below is a nonlimiting list of transfer agents: isopropyl alcohol,sodium hypophosphite, mercaptoethanol, etc.

The process will be successfully used for the manufacture of packingpapers and paperboards, coating base papers, sanitary and domesticpapers, and any type of papers, paperboards or the like requiring theuse of a polymer as a dry strength, retention, drainage and runnabilityaid.

The term “runnability” denotes the optimization of the operation of thepapermaking machine by increasing the productivity via better drainagethrough the table, better dryness in the press section, a reduction inbreaks through a greater cleanliness of the circuits and a reduction indeposits.

The process furthermore makes it possible to obtain good drainageproperties and good physical properties (improvement in burst, breakinglength, ring crush test, short span compression test, concora mediumtest, internal cohesion, wet breaking length).

Likewise, the final cationic or amphoteric copolymer used in the processof the invention has a cationic charge density preferably of greaterthan 0.4 meq/g and advantageously of greater than 1.25 meq/g.

In practice, the cationic or amphoteric (co)polymer is derived from thereaction between:

-   -   from 1 to 30 wt % of at least one aldehyde preferably selected        from the group consisting of glyoxal, glutaraldehyde,        furandialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, di        aldehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, and        combinations thereof,    -   with at least one base (co)polymer optionally branched by means        of a radical branching agent and containing:        -   at least 5 mol % of a nonionic monomer selected from the            group consisting of acrylamide (and/or methacrylamide),            N,N-dimethylacrylamide, and/or acrylonitrile, preferably            acrylamide,        -   at least 100 ppm of at least one additional polyfunctional            compound selected from the group consisting of            polyethyleneimine, polyamine (primary or secondary),            polyallylamine, polythiols, polyalcohols,            polyamide-epichlorohydrin (PAE) resins and polyamine amides            (PAA), advantageously polyethyleneimine,        -   optionally at least:            -   one unsaturated cationic ethylenic monomer, preferably                selected from the group consisting of monomers of                dialkylaminoalkyl (meth)acrylamide, diallylamine and                methyldiallylamine type and the quaternary ammonium or                acid salts thereof. Mention will in particular be made                of diallyldimethylammonium chloride (DADMAC),                acrylamidopropyltrimethylammonium chloride (APTAC)                and/or methacrylamidopropyltrimethyl ammonium chloride                (MAPTAC),            -   and/or a nonionic monomer preferably selected from the                group consisting of N-vinyl acetamide, N-vinyl                formamide, N-vinylpyrrolidone and/or vinyl acetate,            -   and/or an anionic monomer of acid or anhydride type                selected from the group consisting of (meth)acrylic                acid, acrylamidomethylpropylsulphonic acid, itaconic                acid, maleic anhydride, maleic acid, methallylsulphonic                acid, vinylsulphonic acid and salts thereof.

Advantageously, the final cationic or amphoteric (co)polymer is derivedfrom the reaction preferably between:

-   -   15 to 25 wt % of glyoxal,    -   a base (co)polymer branched by means of a radical branching        agent and comprising:        -   at least 5 mol % of acrylamide,        -   at least 100 ppm of polyethyleneimine,        -   5 to 50 mol % of at least one unsaturated cationic ethylenic            comonomer, selected from the group consisting of monomers of            dialkylaminoalkyl (meth)acrylamide, diallylamine and            methyldiallylamine type and the quaternary ammonium or acid            salts thereof, preferably diallyldimethylammonium chloride,        -   at least 100 ppm of a radical branching agent.

It should be noted that, in combination with these monomers, it is alsopossible to use monomers that are insoluble in water, such as acrylic,allyl or vinyl monomers comprising a hydrophobic group. During the usethereof, these monomers will be employed in very small amounts, of lessthan 20 mol %, preferably less than 10 mol %, and they will preferablybe selected from the group consisting of acrylamide derivatives such asN-alkylacrylamides, for example N-tert-butylacrylamide andoctylacrylamide, and also N,N-dialkylacrylamides such asN,N-dihexylacrylamide, and acrylic acid derivatives such as alkylacrylates and methacrylates.

According to a preferred embodiment, the base copolymer used in theinvention is a copolymer of a nonionic monomer and a cationic monomer.

The incorporation of the additional polyfunctional compound thatmodifies the structure of the base (co)polymer could be carried out inthe reaction medium before or during the polymerization, or by any othermethod of grafting to the finished base copolymer. Advantageously, thepolyfunctional compound does not react with the monomers before theirpolymerisation.

Preferably, the additional polyfunctional compound will be mixed with acomonomer before polymerization.

Advantageously, during the process, the amount of final (co)polymerintroduced into the fibre suspension is between 500 and 4000 grams ofactive polymer per tonne of dry pulp (g/t). Preferably, the amountintroduced is between 1000 g/t and 3000 g/t.

The base (co)polymer does not require the development of a particularpolymerization process. The principal polymerization techniques, wellknown to a person skilled in the art, and which may be used are:precipitation polymerization, emulsion (aqueous or inverse)polymerization, which may or may not be followed by a distillationand/or spray-drying step, and suspension polymerization or solutionpolymerization, these two techniques being preferred.

Glyoxalation does not require a particular method. The principalglyoxalation techniques known to a person skilled in the art can beused. For example, the pH could be adjusted after addition of glyoxalwith a solution of sodium hydroxide. It is also possible to conduct thereaction at a pH that is controlled by a continuous addition of sodiumhydroxide, but also to add the glyoxal in several fractions. Theprogress of the reaction could also be monitored by measuring theviscosity, turbidity, etc.

According to the invention, the additive is added to the process beforeor after formation of the sheet. Thus, the cellulosic material can bebrought into contact with the additive in various ways. The final(co)polymer could be used in the form of a diluted or undiluted aqueoussolution. It will be added to the cellulosic material. It could beapplied by an impregnation technique or could be directly added to thefibre suspension at any point of the paper manufacturing process wheredry strength aids are customarily introduced.

It could be introduced into the thick stock or into the thin stock. Itcould be added at the fan pump or headbox. Preferably, the (co)polymerwill be introduced before the headbox.

It could also be added at the wire end or size press, for example byspraying.

The incorporation or application of the final (co)polymer will becarried out with conventional means known to person skilled in the art.

Preferably, the final (co)polymer is injected industrially into thefibre suspension, i.e. before the dilution thereof by the white waters(thick stock). The concentrations of the stock or pulp are of the orderof 3% and 5%.

The process could be used with virgin fibre (Kraft, bisulfite, etc.)stocks or pulps or recycled fibre stocks or pulps, deinked stocks orpulps, mechanical stocks or pulps and thermomechanical stocks or pulps.

The final (co)polymer could be prepared in the vicinity of thepapermaking machine.

The invention and the advantages that result therefrom emerge clearlyfrom the following exemplary embodiments.

Exemplary Embodiments

Protocol for the Synthesis of the Compound of the Invention

Synthesis of Modified Base (Co)Polymer with PEI During Polymerization

The polymers of the invention identified from polymers 1 to 17 wereobtained from a modified base copolymer with PEI during polymerizationaccording to the following protocol.

The examples were carried out with an acrylamide/diallyldimethylammoniumchloride (DADMAC) copolymer, branched with MBA (1000 ppm/activematerial), modified with a polyethyleneimine polymer (of Polymin HM typeby BASF), in a proportion of 1% with respect to the active material. Inorder to do this, the polyethyleneimine is mixed with the DADMAC monomerand with the MBA in the reactor. The acrylamide will be incorporated bydripping continuously, over 2 h, into a reaction medium maintained at85° C. The catalysis will take place with SPS and MBS, catalysts thatare well known to a person skilled in the art.

Synthesis of the Base (Co)Polymer with Post-Grafting of PEI

In the case of the post-grafting of the (co)polymer, the examples(polymers 19 and 20) were carried out in the same way as above, exceptfor the difference that the polyethyleneimine is not mixed with amonomer in the reactor. In order to do this, the polyethyleneimine isadded to the reactor after the polymerization in a proportion of 1% withrespect to the active material. The grafting takes place by catalysiswith the aid of 1500 ppm of SPS dripping continuously over 1 h 30 min.

Glyoxalation

Introduced into a 600 ml stirred reactor are 154.3 g of base copolymer(20% concentration, 3800 cps) and 626.6 g of demineralised water. Thereactor is equipped with a pH measurement probe. After stirring for 10minutes, the pH is adjusted to 10.5 with a 10% sodium hydroxidesolution. The temperature is maintained between 24° C. and 26° C.

19.0 g of 40% glyoxal are added. The pH value is 8.75. Controlling thepH and monitoring the viscosity make it possible to obtain a product of52 cps after 65 minutes of reaction. When the desired viscosity isachieved, the reaction is stopped by lowering the pH to less than 3.5 byaddition of 92% H₂SO₄.

The pH may be adjusted after addition of glyoxal with a 10% sodiumhydroxide solution. It is possible to carry out the reaction at a pHthat is controlled by continuous addition of 10% sodium hydroxide, butalso to add the glyoxal in several fractions.

The viscometer used is of Brookfield type, with an LV1 spindle and aspeed of 60 rpm.

Pulp Preparation

The pulp used consists of recycled paperboard fibres. The paper pulp isprepared by disintegrating, over 30 minutes, 90 grams of recycled fibresin 2 liters of hot water. The Shopper degree of the pulp thus obtainedis 43. The tests are carried out with the pulp at neutral pH. The pulpobtained is then diluted to a total volume of 9 liters. Once theconsistency has been accurately measured, the required amount of thispulp is withdrawn so as to obtain, in the end, a sheet with a basisweight of 120 g/m².

Test of the Polymer Properties

A/ Drainage Performances

CSF sequence at 1000 rpm (revolutions per minute):

Use of a static handsheet former for stirring the pulp. Introduction of1 liter of 0.3% pulp.

T=0 s: stirring of the pulp.

T=10 s: addition of polymer.

T=30 s: cessation of stirring and recovery of the liter of pulp.Implementation of the TAPPI T 227OM-94 test.

CSF: measure of the degree of “drainability” of the pulp

B/ Performances in DSR (Dry Strength) Application, Basis Weight at 60g/m²

1/ Sheet Formation

The paper handsheets are produced with an automatic dynamic handsheetformer. The pulp is introduced into the chest of the dynamic handsheetformer, diluted to a consistency of 0.32% and gently stirred with amechanical stirrer in order to homogenize the fibre suspension. Inmanual mode, the pulp is pumped up to the level of the nozzle in orderto prime the circuit. A blotting paper and the forming fabric are placedin the drum of the dynamic handsheet former before starting the rotationof the drum at 900 m/min and constructing the water wall. The finalcopolymer is then introduced into the agitated fibre suspension with acontact time of 30 seconds. The sheet is then produced (in automaticmode) by 22 to-and-fro movements of the nozzle spraying the pulp intothe water wall. Once the water is drained and once the automaticsequence is completed, the forming fabric with the network of fibresformed is removed from the drum of the dynamic handsheet former andplaced on a table. A dry blotting paper is placed on the side of the matof wet fibres and is pressed once with a roller. The assembly is turnedover and the fabric is carefully separated from the fibrous mat. Asecond dry blotting paper is placed and the sheet (between the twoblotting papers) is pressed once under a press delivering 4 bar and isthen dried on a stretched dryer for 9 min at 107° C. The two blottingpapers are subsequently removed and the sheet is stored overnight in achamber with controlled humidity and controlled temperature (50%relative humidity and 23° C.). The dry strength properties of all of thesheets obtained via this procedure are then evaluated.

2/ Bursting Test

The burst index is measured with a Messmer Buchel M 405 burstingstrength tester (average over 14 measurements). The test is carried outaccording to the standard TAPPI T403 OM 91

3/ Dry Tensile Strength Test

The breaking length is measured using a Testometric AXM250 tensiletesting machine. The test is carried out according to the standard TAPPI494 OM 88.

Modified base (co)polymer with PEI during polymerization

In all the examples that follow, and unless otherwise indicated, thesheets of paper are produced according to the above procedure byintroducing the final copolymer at a dosage of 2.5 kg/T (dry polymer/dryfibre).

TABLE 1 characteristics and results of the tests of the high viscositypolymers Dosage: 1.5 kg/T Dosage: 2.5 kg/T Glyoxalated MBA PEI Dry DryBase Base product (ppm/ (ppm/ tensile tensile cationicity viscosityviscosity MA MA CSF Burst strength CSF Burst strength Polymers (mol %)(cPs) (cPs) base) base) (ml) index (km) (ml) index (km) Blank 270 1.993.82 270 1.99 3.82 Polymer 2 15% 3700 50.5 0 0 420 2.28 4.24 488 2.564.71 Polymer 3 15% 3250 52.0 1000 0 431 2.25 4.12 495 2.27 4.40 Polymer4 15% 3800 53.0 1000 1000 440 2.32 4.65 504 2.58 4.77 (invention)

The branching alone of the glyoxalated and PEI-free base copolymer(polymer 3) makes it possible to obtain an improvement in the drainageproperties but is prejudicial to the improvement in the physicalproperties. The process of the invention itself makes it possible toobtain an improvement in the drainage that is greater than the otherproducts while retaining, or even while improving the physicalproperties in the dry state.

TABLE 2 characteristics and results of the tests of the low viscositypolymers Glyoxalated MBA PEI Base Base product (ppm/ (ppm/ Breakingcationicity viscosity viscosity MA MA CSF Burst length Polymers (mol %)(cPs) (cPs) base) base) (ml) index (km) Blank 272 1.69 3.28 Polymer 515% 485 51.5 0  0 465 2.29 4.89 Polymer 6 15% 720 52.0 1000  0 468 2.234.82 Poly's mer 7 15% 500 49.0 1000 1000  489 2.32 4.97 (invention)Polymer 8a 15% 485 49.0 0 1000*  454 2.27 4.90 Polymer 8b 15% 485 49.5 01000** 453 2.25 4.85 1000* PEI added to the copolymer that has reactedwith the aldehyde compound. 1000** PEI added to the copolymer beforereaction with the aldehyde compound. It is not a grafting requiringspecific reaction conditions. The PEI is simply mixed with thecopolymer.

This second series of tests demonstrates that the tendency to improvethe results remains identical during the use of base copolymers of lowerviscosity (polymers 5 and 6). The results obtained with polymer 8a and8b are inferior to those of the polymer of the invention. These resultsdemonstrate the importance of the presence of PEI during thepolymerization of the base copolymer and its incorporation into thestructure of the base copolymer.

TABLE 3 characteristics and results of the tests of the polymers of theinvention with an increase in cationicity. Glyoxalated MBA PEI Base Baseproduct (ppm/ (ppm/ Breaking cationicity viscosity viscosity MA MA Burstlength Polymers (mol %) (cPs) (cPs) base) base) CSF index (km) Blank 2771.82 3.90 Polymer 9  5% 2050 43.5 0 0 341 2.14 4.53 Polymer 10  5% 120050.5 1000 1000 355 2.17 4.73 Polymer 11 15% 3800 53.0 1000 1000 445 2.364.95 Polymer 12 30% 4200 50.5 1000 1000 449 2.46 4.86 Polymer 13 30%3850 51.5 0 0 430 2.32 4.72 Polymer 14 40% 1600 48.5 1000 1000 448 2.384.73

The above table shows the change in the results with respect to theincrease in the cationicity of the base polymer. The polymers of theinvention are all better than polymer 9.

By comparing the performances of polymers 9 and 10 having the samecationicity, it is surprisingly observed that with a lower molecularweight within the context of the invention (polymer 10), it is possibleto obtain better drainage and dry strength results.

With a similar molecular weight (base copolymer), polymers 10 and 14have different performances. Polymer 14, which has a cationicity of 40mol %, gives superior results, whether it be in terms of drainage orburst index, than polymer 10 (5 mol % cationicity).

It should be noted that the benefit of the invention appliesirrespective of the cationicity of the product. Indeed, by comparingpolymers 12 and 13, both of the same cationicity (30 mol %), it isobserved that the polymer of the invention (polymer 12) gives betterdrainage and physical property performances.

Glyoxalated MBA PEI Base product (ppm/ (ppm/ Breaking cationicityviscosity MA MA Burst length Polymers (mol %) (cPs) base) base) CSFindex (km) Blank 272.00 1.69 3.28 Polymer 15 30% 42.0 1000 1000 451 2.345.01 Polymer 16 30% 53.0 1000 1000 540 2.19 4.42 Polymer 17 30% 32.0 0 0428 2.16 4.10

Polymer 17 corresponds to example 7 from patent US 2011/0056640 whichhas been reproduced then tested.

The table above shows that two polymers (polymers 15 and 16) derivedfrom the invention, glyoxalated at two different viscosities, haveproperties that are superior to polymer 17, of the same cationicity.

In Case of Base (Co)Polymer Modified with Post-Grafting of PEI

Polymers 19 and 20 were made by post-grafting the base (co)polymer withPEI. Specifically, the polymerization of acrylamide and DADMAC in thepresence of MBA is performed. The obtained polymer is then separatedinto three fractions.

The first fraction reacts with glyoxal as described above: Sample 18.

In the second fraction, the initiator (SPS) and PEI is added bycontinuous casting for 90 minutes at the temperature of 80° C., in orderto post-graft the PEI. This sample has been glyoxalated according to thestandard process: Sample 19.

The third fraction was treated in the same manner as the sample 19, butwithout adding PEI. The aim is to assess the impact of continuous addingof SPS. The glyoxalation is identical to the Examples 18 and 19.

Glyoxalated Base Base product MBA PEI Dosage Dosage: cationicityviscosity viscosity (ppm/MA (ppm/MA 2 kg/T 2.5 kg/T Polymers (mol %)(cPs) (cPs) base) base) CSF (ml) CSF (ml) Polymer 18 22% 1200 125 1000 0453 421 Polymer 19 22% 1200 125 1000 1000 462 432 Polymer 20 22% 1200120 1000 0 441 407

The results (draining by CSF) show again a performance when polymer 18(base polymer without PEI) is compared to polymer 19 (base post-graftedPEI). Polymer 20 has inferior performance compared to polymer 18, withthe indication of a degradation when the SPS is added during 90 minutesat the temperature of 80° C. It is therefore concluded that it is thepost-grafting of the PEI which brings this gain of performance.

The invention claimed is:
 1. A process for manufacturing a sheet ofpaper and/or of paperboard, said process comprising: before or afterformation of said sheet, bringing cellulosic material into contact withat least one additive, wherein said additive is a cationic or amphoteric(co)polymer derived from the reaction between at least one aldehyde andat least one base (co)polymer comprising at least one nonionic monomerselected from the group consisting of acrylamide, methacrylamide,N,N-dimethylacrylamide, and acrylonitrile, said base copolymer beingmodified, prior to the reaction with the at least one aldehyde, with atleast one polyfunctional compound comprising at least three heteroatomschosen from N, S, O and P, in which at least three of these heteroatomseach have at least one mobile hydrogen, wherein the base (co)polymer ismodified with at least one polyfunctional compound either byincorporation of the at least one polyfunctional compound(s) before orduring polymerization of the constituent comonomers of the base(co)polymer, or by grafting of the at least one polyfunctionalcompound(s) to the base (co)polymer, wherein the base (co)polymer, priorto the reaction with the at least one aldehyde, is modified in theabsence of glyoxal, wherein the polyfunctional compound(s) are selectedfrom the group consisting of polyethyleneimines, primary polyamines,secondary polyamines, polyallylamines, polythiols, polyalcohols,polyamide-epichlorohydrin resins and polyamine amides, and wherein thealdehyde is selected from the group consisting of glyoxal,glutaraldehyde furandialdehyde, 2-hydroxyadipaldehyde, succinaldehyde,dialdehyde starch, 2,2-dimethoxyethanal, diepoxy compounds, andcombinations thereof.
 2. The process according to claim 1, wherein thepolyfunctional compound is selected from the group consisting ofpolyethyleneimine and polyamine amide.
 3. The process according to claim2, wherein the base copolymer is branched in the presence of a radicalbranching agent.
 4. The process according to claim 3, wherein theradical branching agent is selected from the group consisting ofmethylenebisacrylamide, ethylene glycol diacrylate, polyethylene glycoldimethacrylate, diacrylamide, cyanomethyl acrylate, vinyloxyethylacrylate or methacrylate, and triallylamine.
 5. The process according toclaim 2, wherein the aldehyde is glyoxal.
 6. The process according toclaim 1, wherein the base copolymer is branched in the presence of aradical branching agent.
 7. The process according to claim 6, whereinthe aldehyde is glyoxal.
 8. The process according to claim 6, whereinthe radical branching agent is selected from the group consisting ofmethylenebisacrylamide, ethylene glycol diacrylate, polyethylene glycoldimethacrylate, diacrylamide, cyanomethyl acrylate, vinyloxyethylacrylate or methacrylate, and triallylamine.
 9. The process according toclaim 8, wherein the final cationic or amphoteric (co)polymer is derivedfrom a reaction between: 15 to 25 wt % of glyoxal, a base (co)polymerbranched by means of a radical branching agent and comprising: at least5 mol % of acrylamide, at least 100 ppm of polyethyleneimine, 5 to 50mol % of at least one unsaturated cationic ethylenic comonomer, selectedfrom the group consisting of monomers of dialkylaminoalkyl(meth)acrylamide, diallylamine and methyldiallylamine type and thequaternary ammonium or acid salts thereof, and at least 100 ppm of aradical branching agent.
 10. The process according to claim 1, whereinthe aldehyde is glyoxal.
 11. The process according to claim 1, whereinthe cationic or amphoteric (co)polymer is derived from the reactionbetween: from 1 to 30 wt % of at least one aldehyde selected from thegroup consisting of glyoxal, glutaraldehyde, furandialdehyde,2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch,2,2-dimethoxyethanal, diepoxy compounds, and combinations thereof, withat least one base (co)polymer optionally branched by means of a radicalbranching agent and containing: at least 5 mol % of a nonionic monomerselected from the group consisting of acrylamide, methacrylamide,N,N-dimethylacrylamide, and/or acrylonitrile, at least 100 ppm of atleast one polyfunctional compound selected from the group consisting ofpolyethyleneimine, primary polyamines, secondary polyaminespolyallylamine, polythiols, polyalcohols, polyamide-epichlorohydrinresins and polyamine amides, optionally at least: one unsaturatedcationic ethylenic monomer, selected from the group consisting ofmonomers of dialkylaminoalkyl (meth)acrylamide, diallylamine andmethyldiallylamine type and the quaternary ammonium or acid saltsthereof, and/or a nonionic monomer selected from the group consisting ofN-vinyl acetamide, N-vinyl formamide, N-vinylpyrrolidone and/or vinylacetate, and/or an anionic monomer of acid or anhydride type selectedfrom the group consisting of (meth)acrylic acid,acrylamidomethylpropylsulphonic acid, itaconic acid, maleic anhydride,maleic acid, methallylsulphonic acid, vinyl sulphonic acid and saltsthereof.
 12. The process according to claim 11, wherein the at least oneadditional polyfunctional compound includes polyethyleneimine.
 13. Theprocess according to claim 11, wherein the optional at least oneunsaturated cationic ethylenic monomer is selected from the groupconsisting of diallyldimethylammonium chloride,acrylamidopropyltrimethylammonium chloride, andmethacrylamidopropyltrimethylammonium chloride.
 14. The processaccording to claim 13, wherein the at least one additionalpolyfunctional compound is selected from the group consisting ofpolyethyleneimine and polyamine amide.
 15. The process according toclaim 1, wherein the final cationic or amphoteric (co)polymer is derivedfrom reaction between: 15 to 25 wt % of glyoxal, a base (co)polymerbranched by means of a radical branching agent and comprising: at least5 mol % of acrylamide, at least 100 ppm of polyethyleneimine, 5 to 50mol % of at least one unsaturated cationic ethylenic comonomer, selectedfrom the group consisting of monomers of dialkylaminoalkyl(meth)acrylamide, diallylamine and methyldiallylamine type and thequaternary ammonium or acid salts thereof, and at least 100 ppm of aradical branching agent.
 16. The process according to claim 15, whereinthe at least one unsaturated cationic ethylenic comonomer includesdiallyldimethylammonium chloride.